cis-(-)-2,3,3a,4,5,9b-hexahydro-9-bromo-3-(1-phenylethenyl)-1H-benz[e]indol-2-one | 180624-35-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: cis-(-)-2,3,3a,4,5,9b-hexahydro-9-bromo-3-(1-phenylethenyl)-1H-benz[e]indol-2-one
• 英文别名: (3aR,9bS)-9-bromo-3-(1-phenylethenyl)-3a,4,5,9b-tetrahydro-1H-benzo[e]indol-2-one
• CAS: 180624-35-5
• 化学式: C₂₀H₁₈BrNO
• 分子量: 368.273
• InChiKey: ODQLWUCKYWFXNE-SJLPKXTDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-(-)-2,3,3a,4,5,9b-hexahydro-9-bromo-3-(1-phenylethenyl)-1H-benz[e]indol-2-one 在 盐酸 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以92%的产率得到cis-(-)-2,3,3a,4,5,9b-hexahydro-9-bromo-1H-benz[e]indol-2-one
  参考文献：
  名称：

  Asymmetric Synthesis of Cis-Fused Bicyclic Pyrrolidines and Pyrrolidinones via Chiral Polycyclic Lactams

  摘要：

  Condensation of racemic keto-ester 2 and 1.1 equiv of (R)-(-)-phenylglycinol in toluene with azeotropic removal of water and methanol gave rise to a tetracyclic lactam in greater than 90% yield. Examination of the crude reaction product by H-1 and C-13 NMR, capillary GC, and HPLC revealed this product to be a single isomer, the absolute configuration of which was determined to be that illustrated by structure 3. The tetracyclic lactam 3 was stereospecifically reduced to either the cis-fused bicyclic pyrrolidine 4 or the cis-fused bicyclic pyrrolidinone 9. The chiral auxiliaries in both 4 and 9 were removed using different, novel methodologies. This highly stereoselective reaction establishes two contiguous chiral centers via the deracemization of an achiral keto-ester. This methodology has been applied to the synthesis of (1R,5R)-2-azabicyclo[3.3.0]octane 15. This important amine is now readily available from commercial materials in only three steps.

  DOI：

  10.1021/jo960185l
• 作为产物：
  描述：

  cis-(-)-2,3,3a,4,5,9b-hexahydro-9-bromo-3-(2(R)-1-hydroxypheneth-2-yl)-1H-benz[e]indol-2-one 在 lithium hydroxide 作用下， 以 二甲基亚砜 为溶剂， 反应 72.0h， 以90%的产率得到cis-(-)-2,3,3a,4,5,9b-hexahydro-9-bromo-3-(1-phenylethenyl)-1H-benz[e]indol-2-one
  参考文献：
  名称：

  Asymmetric Synthesis of Cis-Fused Bicyclic Pyrrolidines and Pyrrolidinones via Chiral Polycyclic Lactams

  摘要：

  Condensation of racemic keto-ester 2 and 1.1 equiv of (R)-(-)-phenylglycinol in toluene with azeotropic removal of water and methanol gave rise to a tetracyclic lactam in greater than 90% yield. Examination of the crude reaction product by H-1 and C-13 NMR, capillary GC, and HPLC revealed this product to be a single isomer, the absolute configuration of which was determined to be that illustrated by structure 3. The tetracyclic lactam 3 was stereospecifically reduced to either the cis-fused bicyclic pyrrolidine 4 or the cis-fused bicyclic pyrrolidinone 9. The chiral auxiliaries in both 4 and 9 were removed using different, novel methodologies. This highly stereoselective reaction establishes two contiguous chiral centers via the deracemization of an achiral keto-ester. This methodology has been applied to the synthesis of (1R,5R)-2-azabicyclo[3.3.0]octane 15. This important amine is now readily available from commercial materials in only three steps.

  DOI：

  10.1021/jo960185l

文献信息

• Asymmetric Synthesis of <i>Cis</i>-Fused Bicyclic Pyrrolidines and Pyrrolidinones <i>via</i> Chiral Polycyclic Lactams
  作者：Michael D. Ennis、Robert L. Hoffman、Nabil B. Ghazal、David W. Old、Pamela A. Mooney

  DOI：10.1021/jo960185l

  日期：1996.1.1

  Condensation of racemic keto-ester 2 and 1.1 equiv of (R)-(-)-phenylglycinol in toluene with azeotropic removal of water and methanol gave rise to a tetracyclic lactam in greater than 90% yield. Examination of the crude reaction product by H-1 and C-13 NMR, capillary GC, and HPLC revealed this product to be a single isomer, the absolute configuration of which was determined to be that illustrated by structure 3. The tetracyclic lactam 3 was stereospecifically reduced to either the cis-fused bicyclic pyrrolidine 4 or the cis-fused bicyclic pyrrolidinone 9. The chiral auxiliaries in both 4 and 9 were removed using different, novel methodologies. This highly stereoselective reaction establishes two contiguous chiral centers via the deracemization of an achiral keto-ester. This methodology has been applied to the synthesis of (1R,5R)-2-azabicyclo[3.3.0]octane 15. This important amine is now readily available from commercial materials in only three steps.